U.S. patent number 4,339,366 [Application Number 06/319,144] was granted by the patent office on 1982-07-13 for process for the production of polyester resins.
Invention is credited to David H. Blount.
United States Patent |
4,339,366 |
Blount |
July 13, 1982 |
Process for the production of polyester resins
Abstract
Polyester resins are produced by chemically reacting a
broken-down alkali metal lignin-cellulose polymer, a substituted
organic hydroxy compound and a polycarboxylic acid compound and/or
a polycarboxylic acid anhydride. Polyester resins may be used as
molding powder, as coating agents and to produce polyurethane
foams.
Inventors: |
Blount; David H. (San Diego,
CA) |
Family
ID: |
26902210 |
Appl.
No.: |
06/319,144 |
Filed: |
November 9, 1981 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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207391 |
Nov 17, 1980 |
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134975 |
Mar 30, 1980 |
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13139 |
Feb 21, 1979 |
4226982 |
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Current U.S.
Class: |
527/100; 521/100;
521/109.1; 521/154; 527/103; 527/105; 527/300; 527/305; 527/311;
527/313; 527/314; 528/44 |
Current CPC
Class: |
C08B
1/08 (20130101); C08B 15/00 (20130101); C08H
8/00 (20130101); C08G 63/12 (20130101); C08G
18/6484 (20130101) |
Current International
Class: |
C08B
1/08 (20060101); C08B 15/00 (20060101); C08B
1/00 (20060101); C08G 63/00 (20060101); C08G
63/12 (20060101); C08G 18/00 (20060101); C08H
5/04 (20060101); C08H 5/00 (20060101); C08G
18/64 (20060101); C08L 001/00 () |
Field of
Search: |
;260/9,17.4R,17.4Cl,22CB,22XA,29.2E,29.6S,29.7S ;521/100,109,154
;528/44 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Foelak; Morton
Parent Case Text
CROSS-REFERENCE TO RELATED COPENDING APPLICATIONS
This application is a continuation-in-part of my copending U. S.
patent application, Ser. No. 207,391, filed on Nov. 17, 1980, which
is a continuation-in-part of my copending U. S. patent application,
Ser. No. 134,975, filed on Mar. 30, 1980, which is a
continuation-in-part of my copending U. S. patent application, Ser.
No. 13,139, filed on Feb. 21, 1979, now U. S. Pat. No. 4,226,982.
Claims
I claim:
1. The process for the production of polyester resinous products by
mixing, heating and reacting the following components:
(a) a broken-down alkali metal lignin-cellulose polymer and/or a
broken-down cellulose polymer produced by mixing 3 parts by weight
of a cellulose-containing plant or plant derivative with 2 to 5
parts by weight of melted alkali metal hydroxide, then heating the
mixture at 150.degree. C. to 220.degree. C. while agitating for 5
to 60 minutes; in an amount of 10 to 50 parts by weight;
(b) a substituted organic hydroxy compound, which contains at least
one substituent which will split off in the reaction, in an amount
of 10 to 50 parts by weight;
(c) polycarboxylic acid or polycarboxylic acid anhydride, or
mixtures thereof, in an amount of 10 to 50 parts by weight.
2. The process of claim 1 wherein the substituted organic hydroxy
compound is a halohydrin compound selected from the group
consisting of ethylene chlorohydrin, ethylene bromohydrin,
glycerine, .alpha.,.gamma.dichlorohydrin and mixtures thereof.
3. The process of claim 1 wherein the polycarboxylic acid is
selected from the group consisting of maleic acid, phthalic acid,
succinic acid, oxalic acid, malonic acid, glutaric acid, adipic
acid, pimelic acid, azelaic acid, suberic acid, isophthalic acid,
fumaric acid, sebacic acid, terephthalic acid, itaconic acid,
diglycolic acid and mixtures thereof.
4. The process of claim 1 wherein the polycarboxylic acid anhydride
is selected from the group consisting of phthalic acid anhydride,
maleic acid anhydride, succinic acid anhydride, glutaric acid
anhydride, poly(adipic anhydride), tetrachlorophthalic acid
anhydride, pyromellitic and anhydride, tetrohydrophthalic acid
anhydride, dodecenylsuccinic acid anhydride, hexadecylsuccinic acid
anhydride, nitrophthalic acid anhydride and mixtures thereof.
5. The process of claim 1 wherein up to 50% by weight of the
polycarboxylic acid or polycarboxylic acid anhydride is replaced
with a vegetable oil, selected from the group consisting of soybean
oil, linseed oil, cottonseed oil, tung oil, fish oil, perilla oil,
oiticica oil, sunflower oil, safflower oil, walnut oil, dehydrated
castor oil, monoglyceride of vegetable oils and mixtures
thereof.
6. The product produced by the process of claim 1.
7. The product produced by the process of claim 5.
8. The process of claim 1 wherein up to 25 parts by weight of a
polyhydroxy organic compound are mixed and reacted with Components
(a), (b) and (c).
9. The process of claim 8 wherein the polyhydroxy organic compound
is selected from the group consisting of ethylene glycol,
diethylene glycol, propylene glycol, butylene glycol, trimethylene
glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene
glycol, polyethylene glycol, polypropylene glycol, Bisphenol A,
resorcinol, glycerol, glycerol monochlorohydrin, trimethylol ethane
and mixtures thereof.
10. The process according to claim 1, wherein an additional step is
taken wherein a catalytic amount of a peroxide initiator; selected
from the group consisting of acetyl benzoyl peroxide, peracetic
acid, methyl ethyl ketone peroxide, cyclohexanone peroxide,
cyclohexyl hypoperoxide, 2,4-dichlorobenzoyl peroxide, cumene
hypoperoxide, tert-butyl hydroperoxide, methyl amyl ketone
peroxide, lauroyl peroxide, benzoyl peroxide, tert-butyl
perbenzoate, di-tert-butyl diperphthalate, p-chlorobenzoyl
peroxide; dibenzol diperoxide and mixtures thereof, is admixed with
the polyester resinous product.
11. The process of claim 1 wherein an additional step is taken
wherein a vinyl monomer, selected from the group consisting of
vinyl acetate, styrene, methacrylic acid, methyl methacrylate,
vinyl toluene, acrylic acid, acrylonitrile, divinyl benzene and
mixtures thereof, in an amount of up to 50% by weight, percentage
based on polyester resinous product, is admixed with the polyester
resinous product of claim 1, then a catalytic amount of a peroxide
initiator and activator is added and is thoroughly mixed and
reacted.
12. The product produced by the process of claim 11.
13. The process of claim 11 wherein the peroxide initiator is
methyl ethyl ketone peroxide in the amount of 0.2% to 0.5% by
weight, percentage based on weight of polyester resinous product,
and the activator is cobalt naphthanate in the amount of 30 to 100
ppm of cobalt metal.
14. The process of claim 1 wherein an organic compound selected
from the group consisting of formaldehyde, substituted organic
compound polyol, vegetable oils, and mixtures thereof, is added
with Components (a), (b) and (c).
15. The product produced by the process of claim 14.
16. The process of claim 14 wherein the substituted organic
compound having a substituent which will split off during the
reaction to said broken-down alkali metal lignin-cellulose and/or a
broken-down cellulose polymer in the amount wherein the mols of the
substituted radicals are about equal to the mols of the alkali
radicals in the mixture, the substituent containing at least one
substituent selected from the group consisting of acid sulfate,
nitrate, sulfate, acid phosphate, bicarbonate, formate, acetate,
propionate, laurate, oleate, stearate, oxalate, acid malonate, acid
tartrate, acid citrate, halogens and mixtures thereof.
17. The process of claim 1 wherein up to 25 parts by weight of
water is added to the broken-down alkali metal lignin-cellulose or
broken-down alkali metal cellulose.
Description
BACKGROUND OF THE INVENTION
This invention relates to a process for the production of polyester
resinous products produced by chemically reacting a broken-down
alkali metal lignin-cellulose polymer, a substituted organic
hydroxy compound and a polycarboxylic acid and/or polycarboxylic
acid anhydride. When an unsaturated polyester resin is to be
produced, an unsaturated substituted organic hydroxy compound or an
unsaturated polycarboxylic acid and/an polycarboxylic acid
anhydride may be used in the reactive mixture.
The polyester resinous product may be utilized as a protective
coating for wood, metal, plastics, linoleum, leather, fabric and
rubber. They may be utilized in paints, lacquers, metal primers,
caulking compounds and water-emulsion paints. The unsaturated
polyester resinous products, when copolymerized with a
polymerizable organic compound, will produce hard, solid, useful
objects or they may be used in conjunction with a reinforcing
filler such as fiberglas fibers, paper or cloth to produce a
laminate of outstanding strength and durability. They may also be
used as a molding powder, as an adhesive and as impregnants. These
resinous products may be further reacted with epihalohydrins and
polyisocyanate compounds to produce resinous products and
foams.
Polyester resinous products may be modified with vegetable oils,
vinyl monomers, aminoplasts, phenoplasts, phenol, melamine,
silicone resins, silicone silicate resins, cellulose nitrate,
polyisocyanates, cyclopentadienes, terpenes, monobasic acids, e.g.,
benzoic acid and p-tert-butyl benzoic acid; may be modified with
natural resins, ethyl cellulose, chlorinated rubber, aldehyde
phenol silicate resins, aldehydes, polyhydroxyl compounds and other
synthetic and modified natural resins. The useful vinyl monomers
include styrene, acrylates, methacrylates, acrylonitrile, and
mixtures thereof.
Polyester resinous products may be produced by reacting the
following components:
(a) Broken-down alkali metal lignin-cellulose polymer and/or
broken-down cellulose polymer;
(b) Substituted organic hydroxy compound which contains at least
one substitute which will split off in the reaction;
(c) Polycarboxylic acid and/or polycarboxylic acid anhydride.
Component (a)
Component (a), a broken-down alkali metal lignin-cellulose product,
is produced by the processes outlined in my copending U. S. patent
application, Ser. No. 13,139, filed on Feb. 21, 1979, now U. S.
Pat. No. 4,226,982, and is incorporated into this invention.
Water-soluble, broken-down, alkali metal lignin-cellulose polymers
and carbohydrates are produced by mixing 3 parts by weight of a
cellulose-containing plant or plant derivative and 2 to 5 parts by
weight of a melted alkali metal hydroxide, then maintaining the
temperature of the mixture at 150.degree. C. to 220.degree. C.
while agitating for 5 to 60 minutes.
Any suitable plant or the products of plants which contain
cellulose may be used in this invention. The plant material is
preferred to be in the form of small dry particles such as sawdust.
Suitable plants include, but are not limited to, trees, bushes,
agricultural plants, weeds, vines, straw, flowers, kelp, algae and
mixtures thereof. Wood is the preferred plant. Commercial and
agricultural waste products may be used, such as stalks, paper,
cotton clothes, bagasses, etc. Wood fibers (wood pulp) with lignin
removed may be used in this invention. Plants that have been
partially decomposed, such as humus, peat, certain soft brown coal,
manure containing cellulose, etc., may also be used in this
invention.
Any suitable alkali metal hydroxide may be used in this invention.
Suitable alkali metal hydroxides include sodium hydroxide,
potassium hydroxide and mixtures thereof. Sodium hydroxide is the
preferred alkali metal hydroxide.
The novel broken-down water-soluble alkali metal lignin-cellulose
polymer produced by the process of this invention differs from the
alkali cellulose polymers produced by the known processes. The
broken-down alkali metal lignin-cellulose polymer is dark-brown to
black in color, has at least one --COH radical removed from each
cellulose molecule, the usual lignin-cellulose bond is not broken
in most of the cases and the cellulose molecules are broken down
into smaller molecules of alkali metal broken-down lignin-cellulose
which are water-soluble. When a cellulose polymer such as cotton or
wood with the lignin removed is reacted with an alkali metal
hydroxide by the process of this invention, a black water-soluble
broken-down alkali metal cellulose polymer is produced; this
polymer may be reacted with a mineral acid until the pH is about 6
and a black, foamed, brokendown cellulose resinous product and
carbohydrates are produced. The foam is produced by the release of
CO.sub.2 which was removed from the cellulose polymer. When a
mineral acid is added to an aqueous solution of the broken-down
alkali metal lignin-cellulose polymer until the pH is about 6, a
black resinous product floats to the top and is recovered and the
carbohydrates are in the solution.
Component (b)
Any suitable organic monohydroxy compound having a substituent
which will split off during the reaction. The substituent can be
halogen, acid sulfate, nitrate, acid phosphate, bicarbonate,
sulfate, formate, acetate, propionate, laurate, oleate, stearate,
and mixtures thereof.
The halohydrins are the preferred organic monohydroxy-substituted
compound. Suitable halohydrins include the alkene halohydrins such
as ethylene chlorohydrin, ethylene bromohydrin, glycerine .alpha.,
.gamma.dichlorohydrin and the like.
Aliphatic nitro alcohols are produced by reacting nitroalkanes with
aldehydes or ketones in the presence of dilute alkali to produce
compounds with the general formula of: ##STR1## wherein R is an
alkane. 2-nitro-1-hydroxy alkane compounds may be used.
Nitro-phenols may be used.
Component (c)
the polycarboxylic acid may be aliphatic, cycloaliphatic, aromatic
and/or heterocyclic and may be substituted, e.g., with halogen
atoms and may be unsaturated; examples include: Succinic acid,
adipic acid, sebacic acid, suberic acid, azelaic acid, phthalic
acid, phthalic acid anhydride, isophthalic acid, tetrahydrophthalic
acid anhydride, trimellitic acid, hexahydrophthalic acid anhydride,
tetrachlorophthalic acid anhydride, endomethylene
tetrahydrophthalic acid anhydride, glutaric acid anhydride, fumaric
acid, maleic acid, maleic acid anhydride, dimeric and trimeric
acid, fatty acid such as oleic acid, optionally mixed with
monomeric fatty acids, di-methylterephthalate and bis-glycol
terephthalate.
Long-chain unsaturated polyester resins may be made from dibasic
acids and dihydric alcohols. Either the dibasic acid or the
dihydric alcohol may be unsaturated. Usually a combination of
unsaturated and saturated bibasic acids and dihydric alcohols is
used to produce the unsaturated polyester resins. Instead of the
dibasic acids, the corresponding polycarboxylic acid esters of
lower alcohols or their mixtures may be used for preparing the
unsaturated polyester resins.
An unsaturated dibasic acid such as maleic acid, maleic acid
anhydride, fumaric acid, itaconic acid or mixtures thereof must be
included in the production of unsaturated polyester resins, except
when an unsaturated alcohol is used.
A portion, up to 50% by weight, of the polycarboxylic acid and/or
polycarboxylic acid anhydride may be replaced by polymerable oils
such as unsaturated fatty acids (or their esters), tung oil,
linseed oil, heated linseed oil, soybean oil, dehydrated castor
oil, tall oil, cottonseed oil, sunflower oil, fish oil, perilla
oil, safflower oil and mixtures thereof.
A portion, up to 50% by weight, of the polycarboxylic acid and/or
polycarboxylic acid anhydride may be replaced with a linear organic
carbonate selected from the group consisting of p-xylene glycol
bis(ethyl carbonate), diethylene glycol bis(allyl carbonate) and
mixtures thereof.
A portion, up to 50% by weight, of the substituted organic
monohydroxy compound and polycarboxylic acid is replaced with an
organic compound containing hydroxyl and carboxylic radicals,
selected from the group consisting of 10-hydroxy undecanoic acid,
2-hydroxy decanoic acid, .omega.-hydroxy pentadeconoic acid and
mixtures thereof.
Any suitable polymerizing monomer may be used with the unsaturated
polyester resin such as, but not limited to, vinyl monomers, allyl
esters, triallyl cyanurate and mixtures thereof.
Styrene is the preferred polymerizing monomer and may be used alone
or in combination with vinyl acetage. Other vinyl monomers may be
used such as acrylic acid compounds and esters, vinyl toluene,
divinyl benzene, acrylonitrile, methacrylonitrile, etc. The vinyl
monomer may be added in an amount of up to 50% by weight,
percentage based on the weight of the polyester silicate resinous
product.
Activators and promoters, used in conjunction with the initiators
such as cobalt which, in the form of its ethyl hexanoate or
naphthanate salt, is a good, general-purpose activator for use with
ketone peroxides, may be added to the unsaturated polyester resin.
Concentration as low as 30 ppm of cobalt metal will activate a
system. Other activators may be added to the unsaturated polyester
resins such as tertiary dialkyl aryl amines, e.g., diethyl aniline,
and aliphatic thiols, e.g., lauryl mercaptan, when acyl peroxides
are used. When alkali metal or ammonium persulfates are used,
ferric sulfate and cupric sulfate may be added to the unsaturated
polyester resin.
An inhibitor, such a p-tert-butyl catechol, hydroquinone, p-nitrose
dimethylaniline or similar compounds, which will increase the
lifetime of the unsaturated polyester resin, may be added to the
unsaturated polyester resin.
Any suitable initiator which will promote the copolymerization of a
solution of an unsaturated linear polymer in a liquid monomer may
be used in this invention. The controlled polymerization of
unsaturated polyester-monomer mixture, in order to yield fully
cured solids, usually requires the use of an initiator.
Any suitable free-radical initiator, such as organic and inorganic
peroxides, azo compounds, alkali metal persulfates, ammonium
persulfate and mixtures thereof, may be used. The fact that the
action of organic peroxide can be modified by activators and
promoters, plus their ready availability at reasonable cost, makes
them preferable in this invention. Thermal and photopolymerization
may be used in certain cases.
Suitable organic peroxide initiators include, but are not limited
to, acetyl benzoyl peroxide, peracetic acid, methyl ethyl ketone
peroxide, cyclohexanone peroxide, cyclohexyl hydroperoxide,
2,4-dichlorobenzoyl peroxide, cumene hydroperoxide, tert-butyl
hypoperoxide, methyl amyl ketone peroxide, lauroyl peroxide,
benzoyl peroxide, tert-butyl perbenzoate, di-tert-butyl
diperphthalate and mixtures thereof. The amount of organic peroxide
needed to promote the catalytic reaction is quite varied; usually
less than 1%, based on the weight of the reactants, is needed.
Methyl ethyl ketone peroxide is added in an amount of 0.2 to 0.1%
by weight, based on weight of the polyester resinous product.
Any suitable polyhydric alcohol may be used such as, for example,
ethylene glycol; propylene-1,2- and -1,3-glycol; butylene-1,4- and
-2,3-glycol; hexane-1,6-diol; octane-1,8- diol; neopentyl glycol;
cyclohexanedimethanol (1,4-bis-hydroxy-methylcyclohexane); 2-
methylpropane-1,3-diol; glycerol; tri-methylol propane;
hexane-1,2,6-triol; butane-1,2,4-triol; trimethylol ethane,
pentaerythritol; quinitol; mannitol and sorbitol; methylglycoside;
diethylene glycol; triethylene glycol; tetraethylene glycol;
polyethylene glycols; dipropylene glycol; polypropylene glycols;
dibutylene glycol and polybutylene glycols. The polyesters may also
contain a proportion of carboxyl end groups. Polyesters of
lactones, such as c-caprolactone, or hydroxycarboxylic acid such as
.omega.-hydroxycaproic acid, may also be used.
The polyethers with at least 2, generally from 2 to 8 and,
preferably, 2 or 3, hydroxyl groups used according to the invention
are known and may be prepared, e.g., by the polymerization of
epoxides, e.g., ethylene oxide, propylene oxide, butylene oxide,
tetrahydrofurane oxide, styrene oxide or epichlorohydrin, each with
itself, e.g., in the presence of BF.sub.3, or by addition of these
epoxides, optionally as mixtures or successively, to starting
components which contain reactive hydrogen atoms such as alcohols
or amines, e.g., water, ethylene glycol; propylene-1,3- or
1,2-glycol; trimethylol propane; 4,4-dihydroxydiphenylpropane;
aniline, ammonia, ethanolamine or ethylenediamine; sucrose
polyethers such as those described, e.g., in German
Auslegeschriften Nos. 1,176,358 and 1,064,938 may also be used
according to the invention. It is frequently preferred to use
polyethers which contain predominantly primarily OH groups (up to
90% by weight, based on the total OH groups contained in the
polyether). Polyethers modified with vinyl polymers such as those
which may be obtained by polymerizing styrene or acrylonitrites in
the presence of polyethers (U.S. Pat. Nos. 3,383,351; 3,304,273;
3,523,093 and 3,110,695; and German Pat. No. 1,152,536) and
polybutadienes which contain OH groups are also suitable.
By "polythioethers" are meant, in particular, the condensation
products of thiodiglycol with itself and/or with other glycols,
dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino
alcohols. The products obtained are polythiomixed ethers or
polythioether ester amides, depending on the co-component.
The polyacetals used may be, for example, the compounds which may
be obtained from glycols, 4,4'-dihydroxydiphenyl-methylmethane,
hexanediol, and formaldehyde. Polyacetals suitable for the
invention may also be prepared by the polymerization of cyclic
acetals.
The polycarbonates with hydroxyl groups used may be of the kind,
e.g., which may be prepared by reaction diols, e.g.,
propane-1,3-diol; butane-1,4-diol; and/or hexane-1,6-diol or
diethylene glycol, triethylene glycol or tetraethylene glycol, with
diarylcarbonates, e.g., diphenylcarbonates or phosgene.
The polyester amides and polyamides include, e.g., the
predominantly linear condensates obtained from polyvalent saturated
and unsaturated carboxylic acids or their anhydrides, any
polyvalent saturated unsaturated amino alcohols, diamines,
polyamines and mixtures thereof.
Polyhydroxyl compounds which contain urethane or urea groups,
modified or unmodified natural polyols, e.g., castor oil,
carbohydrates and starches, may also be used. Additional products
of alkylene oxides with phenol formaldehyde resins or with
urea-formaldehyde resins are also suitable for the purpose of the
invention.
Polyhydric alcohols of lower molecular weight are preferred, such
as ethylene glycol, diethylene glycol and propylene glycol.
Any suitable aldehyde compound may be reacted with the broken-down
alkali metal lignin-cellulose polymer, then with a substituted
organic hydroxy compound or may be reacted at the same time that
the substituted organic hydroxy compound is reacting with the
alkali metal lignin-cellulose polymer and polycarboxylic acid.
Suitable aldehydes include, but are not limited to, formaldehyde,
acetaldehyde, propionic aldehyde, furfural, crotonaldehyde,
acrolein, butyl aldehyde, paraformaldehyde, pentanals, hexanals,
heptanals and mixtures thereof in the ratio of 1 to 5 parts by
weight of the aldehyde to 2 parts by weight of the broken-down
alkali metal lignin-cellulose polymer. The aldehyde is mixed with
the water-soluble broken-down alkali metal lignin-cellulose
polymer, then agitated at a temperature between ambient temperature
and the boiling temperature of the aldehyde and at ambient pressure
for 10 to 120 minutes, thereby producing an aldehyde alkali metal
lignin-cellulose polymer. The aldehyde-alkali metal
lignin-cellulose polymer is then mixed with a substituted organic
hydroxy compound having a substituent which will split off during
the reaction, to said aldehyde-alkali metal lignin-cellulos polymer
in the amount wherein the mols of the substituted radicals are
about equal to the mols of the alkali radicals in the mixture, then
heated to a temperature between ambient temperature and the boiling
temperature of the reactants while agitating at an ambient pressure
to 1500 psi for about 30 minutes; the reaction is complete in 30
minutes to 8 hours, thereby producing a broken-down organic
lignin-cellulose polymer.
Any suitable organic compound that will react with the broken-down
alkali metal cellulose polymer may be used. Preferred is an organic
compound, having at least one carbon atom which is attached to a
substituent, which is split off during the reaction. These organic
compounds which are the reactants used in the preparation of
broken-down cellulose copolymers have the graphical skeleton carbon
structure of
where
represents two adjacent carbon atoms, or
where X and X represent the substituents which split off during the
reaction. The R between the pair of reactive carbon atoms is
selected from the following groups: Saturated straight-chain carbon
atoms, unsaturated carbon atoms, either linkages, aromatic
structures and others, for it is to be understood that other
intervening structures may be employed. The X and X substituents
can be halogen, acid sulfate, nitrate, acid phosphate, bicarbonate,
formate, acetate, propionate, laurate, oleate, stearate, oxalate,
acid malonate, acid tartrate, acid citrate and others.
The organic compounds which have the graphical skeleton carbon
structure of ##STR2## where X represents the substituents which
split off during the reaction may be used in this invention. The R,
R' and R" are selected from the following groups: Hydrogen,
saturated straight-chain carbon atoms, unsaturated carbon atoms,
ether linkages, aromatic structures, another X and others, for it
is to be understood that other structures may be employed. The X
substituents can be halogen, acid sulfate, nitrate, acid phosphate,
bicarbonate, sulfate formate, acetate, propionate, laurate, oleate,
stearate, acid oxalate, acid malonate, acid tartrate, acid citrate,
mixtures thereof and others.
Suitable substituted organic compounds include, but are not limited
to, substituted alkyl compounds such as methyl halides such as
methyl chloride, methyl bromide, methyl iodide, etc., methyl
sulfate, methyl hydrogen sulfate, methyl hydrogen phosphate, methyl
nitrate; ethyl halides such as ethyl chloride, ethyl bromide, ethyl
iodide, etc., ethyl hydrogen sulfate, ethyl sulfate, ethyl hydrogen
phosphate, ethyl nitrate, ethyl oxalate; propyl halides, propyl
hydrogen sulfate, 1-nitropropane, 2-nitropropane, propyl hydrogen
phosphate; butyl halides, butyl hydrogen sulfate,
2-nitro-1-butanol, butyl hydrogen phosphate, etc.; substituted
unsaturated compounds such as vinyl chloride, vinyl bromide, vinyl
acetate, vinylidine chloride; substituted carboxylic acids such as
chloroacetic acid, dichloroacetic acid, sodium chloroacetate,
bromoacetic acid, iodoacetic acid, .gamma.-chloropropionic acid,
.alpha.-chlorobutyric acid, etc.; acid chlorides such as acetyl
chloride, acetyl bromide, propionyl chloride, n-butyryl chloride,
chloroacetic chloride, etc.; substituted allyl halides such as
allyl halide, methyl allyl halide, etc.; carboxyl acid anhydrides
such as acetic anhydride, propionic anhydride, n-butyric anhydride,
isobutyric anhydride, etc.; organic esters such as ethyl acetate,
methyl propionate, propyl formate, methyl formate, ethyl formate,
methyl acetate, n-butyl acetate, ethyl chloroacetate, etc.; and
substituted hydroxyl.
Some of the useful halogenated compounds include methylene chloride
or bromide, ethylene dichloride, ethylene dibromide, propylene
dichloride or dibromide, epihalohydrins, dihalides of unsaturated
hydrocarbon gases derived from pressure-cracking processes, natural
gas-cracking processes as well as compounds having more than two
substituents such as 1,1,2-trichloroethane; 1,2,4-trichlorobutane;
1,2,3,4-tetrachlorobutane; trichloromesitylene and the like.
Mixtures of these compounds may be used in this process.
Any suitable inorganic or organic solvent may be used in this
invention. Suitable solvents include, but are not limited to,
water, alcohols such as methyl alcohol, ethyl alcohol, isopropyl
alcohol and propyl alcohol.
Any suitable salt-forming compound may be used in this invention to
react with the broken-down alkali metal lignin-cellulose polymer.
Suitable salt-forming compounds include mineral acids such as
hydrochloric acid, sulfuric acid and nitric acid, organic acid such
as acetic acid, propionic acid, etc., and hydrogen-containing acid
salts such as sodium hydrogen sulfate, potassium hydrogen sulfate,
sodium dihydrogen phosphate and potassium dihydrogen phosphate, and
mixtures thereof.
The polyester resinous products of this invention will react with
polyisocyanates such as crude MDI to produce resinous products
which may be used as adhesives, putty caulking agents, etc., and
foams which may be used for thermal and sound insulation.
Any suitable organic polyisocyanate may be used according to the
invention, including aliphatic, cycloaliphatic, araliphatic,
aromatic and heterocyclic polyisocyanates and mixtures thereof.
Suitable polyisocyanates which may be employed in the process of
the invention are exemplified by the organic diisocyanates which
are compounds of the general formula:
wherein R is a divalent organic radical such as an alkylene,
aralkylene or arylene radical. Such suitable radicals may contain,
for example, 2 to 20 carbon atoms. Examples of such diisocyanates
are:
tolylene diisocyanate,
p,p'-diphenylmethane diisocyanate,
phenylene diisocyanate,
m-xylylene diisocyanate,
chlorophenylene diisocyanate,
benzidene diisocyanate,
naphthylene diisocyanate,
decamethylene diisocyanate,
hexamethylene diisocyanate,
pentamethylene diisocyanate,
tetramethylene diisocyanate,
thiodipropyl diisocyanate,
propylene diisocyanate, and
ethylene diisocyanate.
Other polyisocyanates, polyisothiocyanates and their derivatives
may be equally employed. Fatty diisocyanates are also suitable and
have the general formula: ##STR3## where x+y totals 6 to 22 and z
is 0 to 2, e.g., isocyanastearyl isocyanate.
It is generally preferred to use commercially readily-available
polyisocyanates, e.g., tolylene-2,4- and -2,6-diisocyanate and any
mixtures of these isomers, commercially known as "TDI";
polyphenylpolymethylene-isocyanates obtained by
aniline-formaldehyde condensation followed by phosgenation,
commercially known as "crude MDI"; and modified polyisocyanate
containing carbodiimide groups, allophanate groups, isocyanurate
groups, urea groups, imide groups, amide groups or biuret groups,
said modified polyisocyanates prepared by modifying organic
polyisocyanates thermally or catalytically by air, water,
urethanes, alcohols, amides, amines, carboxylic acids, or
carboxylic acid anhydrides, phosgenation products of condensates or
aniline or anilines alkyl-substituted on the nucleus with
formaldehydes or ketones may be used in this invention. Solutions
of distillation residues accumulating during the production of
tolylene diisocyanates, diphenyl methane diisocyanates, or
hexamethylene diisocyanate, in monomeric polyisocyanates or in
organic solvents or mixtures thereof may be used in this invention.
Organic triisocyanates such as triphenylmethane triisocyanate may
be used in this invention. Cycloaliphatic polyisocyanates, e.g.,
cyclohexylene-1,2-; cyclohexylene-1,4-; and
methylene-bis-(cyclohexyl-4,4'-) diisocyanate may be used in this
invention. Suitable polyisocyanates which may be used according to
the invention are described by W. Siefkin in Justus Liebigs Annalen
der Chemie, 562, pages 75 to 136. Inorganic polyisocyanates are
also suitable according to the invention.
Organic polyhydroxyl compounds (polyols) may be used in this
invention with polyisocyanates or may be first reacted with a
polyisocyanate to produce isocyanate-terminated polyurethane
prepolymers and then also be used in this invention.
Reaction products of from 50 to 99 mols of aromatic diisocyanates
with from 1 to 50 mols of conventional organic compounds with a
molecular weight of, generally, from about 200 to about 10,000
which contain at least two hydrogen atoms capable of reacting with
isocyanates, may also be used. While compounds which contain amino
groups, thiol groups, carboxyl groups or silicate groups may be
used, it is preferred to use organic polyhydroxyl compounds, in
particular, compounds which contain from 2 to 8 hydroxyl groups,
especially those with a molecular weight of from about 800 to about
10,000 and, preferably, from about 1,000 to about 6,000, e.g.,
polyesters, polyethers, polythioethers, polyacetals, polycarbonates
or polyester amides containing at least 2, generally from 2 to 8,
but, preferably, dihydric alcohols, with the optional addition of
trihydric alcohols, and polybasic, preferably dibasic, carboxylic
acids. Instead of the free polycarboxylic acids, the corresponding
polycarboxylic acid anhydrides or corresponding polycarboxylic acid
esters of lower alcohols or their mixtures may be used for
preparing the polyesters. The polycarboxylic acid may be aliphatic,
cycloaliphatic, aromatic and/or heterocyclic and may be
substituted, e.g., with halogen atoms and may be unsaturated.
Examples include: Succinic acid, adipic acid, sebacic acid, suberic
acid, azelaic acid, phthalic acid, phthalic acid anhydride,
isophthalic acid, tetrahydrophthalic acid anhydride, trimellitic
acid, hexahydrophthalic acid anhydride, tetrachlorophthalic acid
anhydride, endomethylene tetrahydrophthalic acid anhydride,
glutaric acid anhydride, fumaric acid, maleic acid, maleic acid
anhydride, dimeric and trimeric fatty acid such as oleic acid,
optionally mixed with monomeric fatty acids, dimethylterephthalate
and bis-glycol terephthalate. Any suitable polyhydric alcohol may
be used, such as, for example, ethylene glycol, propylene-1,2- and
-1,2-glycol; butylene-1,4- and -2,3-glycol; hexane-1,6-diol;
octane-1,8-diol; neopentyl glycol;
cyclohexanedimethanol-(1,4-bis-hydroxymethylcyclohexane);
2-methylpropane-1,3-diol; glycerol; trimethylol propane;
hexane-1,2,6-triol; butane-1,2,4-triol; trimethylol ethane;
pentaerythritol; quinitol; mannitol and sorbitol; methylglycoside;
diethylene glycol; triethylene glycol; tetra ethylene glycol;
polyethylene glycols; dipropylene glycol; polypropylene glycols;
dibutylene glycol and polybutylene glycols. The polyesters may also
contain a proportion of carboxyl end groups. Polyesters of lactones
such as c-caprolactone, or hydroxycarboxylic acid such as
c-hydroxycaproic acid may also be used.
The polyethers with at least 2, generally from 2 to 8 and,
preferably, 2 or 3, hydroxyl groups used according to the invention
are known and may be prepared, e.g., by the polymerization of
epoxides, e.g., ethylene oxide, propylene oxide, butylene oxide,
tetrahydrofurane oxide, styrene oxide or epichlorohydrin, each with
itself, e.g., in the presence of BF.sub.3 or by addition of these
epoxides, optionally as mixtures or successively, to starting
components which contain reactive hydrogen atoms such as alcohols
or amines, e.g., water, ethylene glycol; propylene-1,3- or
-1,2-glycol; trimethylol propane; 4,4-dihydroxydiphenylpropane;
aniline; ammonia; ethanolamine or ethylenediamine; sucrose
polyethers, such as those described in German Auslegeschrifren Nos.
1,176,358 and 1,064,938, may also be used according to the
invention. It is frequently preferred to use polyethers which
contain, predominantly, primarily OH groups (up to 90% by weight,
based on the total OH groups contained in the polyether).
Polyethers modified with vinyl polymers such as those which may be
obtained by polymerizing styrene or acrylonitrites in the presence
of polyethers, (U.S. Pat. Nos. 3,383,351; 3,304,273; 3,523,093 and
3,110,695; and German Patent No. 1,152,536) and polybutadienes
which contain OH groups are also suitable.
By "polythioethers" are meant, in particular, the condensation
products of thiodiglycol with itself and/or with other glycols,
dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino
alcohols. The products obtained are polythiomixed ethers or
polythioether ester amides, depending on the co-component.
The polyacetals used may be, for example, the compounds which may
be obtained from glycols, 4,4'-dihydroxydiphenylmethylemethane,
hexanediol and formaldehyde. Polyacetals suitable for the invention
may also be prepared by the polymerization of cyclic acetals.
The polycarbonates with hydroxyl groups used may be of the kind,
e.g., which may be prepared by reaction diols, e.g.,
propane-1,3-diol; butane-1,4-diol; and/or hexane-1,6-diol or
diethylene glycol, triethylene glycol or tetraethylene glycol, with
diarylcarbonates, e.g., diphenylcarbonates or phosgene.
The polyester amides and polyamides include, e.g., the
predominantly linear condensates obtained from polyvalent saturated
and unsaturated carboxylic acids or their anhydrides, any
polyvalent saturated and unsaturated amino alcohols, diamines,
polyamines and mixtures thereof.
Polyhydroxyl compounds which contain urethane or urea groups,
modified or unmodified natural polyols, e.g., castor oil, wood
particles, cellulose, modified cellulose, carbohydrates and
starches, may also be used. Additional products of alkylene oxides
with phenol formaldehyde resins or with urea-formaldehyde resins
are also suitable for the purpose of the invention.
Organic hydroxyl silicate compound as produced in U.S. Pat. No.
4,139,549 may also be used in this invention to react with the
polyisocyanates.
Examples of these compounds which are to be used according to the
invention have been described in High Polymers, Volume XVI,
"Polyurethanes, Chemistry and Technology", published by
Saunders-Frisch Interscience Publishers, New York, London, Volume
I, 1962, pages 32 to 42 and pages 44 to 54, and Volume II, 1964,
pages 5 and 16 and pages 198 and 199; and in Kunststoff-Handbuch,
Volume VII, Vieweg-Hochtlen, Carl-Hanser-Verlag, Munich, 1966, on
pages 45 to 71.
If the polyisocyanates or the prepolymer which contains NCO groups
have a viscosity above 2000 cP at 25.degree. C., it may be
advantageous to reduce the viscosity thereof by mixing it with a
low-viscosity organic polyisocyanate and/or an inert blowing agent
or solvent.
Inorganic polyisocyanates and isocyanate-terminated polyurethane
silicate prepolymers may also be used in this invention.
Polyisocyanate curing agents and/or polyisocyanate activators
(catalysts) may be used in the process of producing polyurethane
resinous or foamed products. The following are examples of
polyisocyanate curing agents and activators:
1. Water.
2. Water containing 10% to 70% by weight of an alkali metal
silicate, such as sodium and/or potassium silicate. Crude
commercial alkali metal silicate may contain other substances,
e.g., calcium silicate, magnesium silicate, borates or aluminates
and may also be used. The molar ratio of alkali metal oxide to
SiO.sub.2 is not critical and may vary within the usual limits, but
is preferably between 4 to 1 and 0.2 to 1.
3. Water containing 20% to 50% by weight of ammonium silicate.
4. Water containing 5% to 40% by weight of magnesium oxide in the
form of a colloidal dispersion.
5. Alkali metal metasilicate such as sodium metasilicate, potassium
metasilicate and commercial dry granular sodium and potassium
silicates. Heating may be required to start the curing
reaction.
6. Water containing 20% to 70% by weight of silica sol.
7. Activators (catalysts) which act as curing agents and are added
to the polyurethane or polyurethane prepolymer in the amount of
0.001% to 10% by weight. They may be added in water.
(a) Tertiary amines, e.g., triethylamine; tributylamine;
N-methyl-morpholine; N,N,N',N'-tetramethylenediamine;
1,4-diazobicyclo-(2,2,2)-octane; N-methyl-N'-dimethylaminoethyl
piperazine; N,N-dimethylbenzylamine;
bis(N,N-diethylaminoethyl)-adipate; N,N-diethylbenzylamine;
pentamethyldiethylenetriamine; N,N-dimethylcyclohexylamine;
N,N,N',N'-tetramethyl-1,3-butanediamine;
N,N-dimethyl-beta-phenylethylamine; and 1,2-dimethylimidazole.
Suitable tertiary amine activators which contain hydrogen atoms
which are reactive with isocyanate groups include, e.g.,
triethanolamine; triisopanolamine; N,N-dimethylethanolamine;
N-methyldiethanolamine; N-ethyldiethanolamine; and their reactive
products with alkylene oxides, e.g., propylene oxide and/or
ethylene oxide and mixtures thereof.
(b) Organo-metallic compounds, preferably organotin compounds such
as tin salts of carboxylic acid, e.g., tin acetate, tin octoate,
tin ethyl hexoate, and tin laurate and the dialkyl tin salts of
carboxylic acids, e.g., dibutyl tin diacetate, dibutyl tin
dilaurate, dibutyl tin maleate or diocyl tin diacetate.
(c) Silaamines with carbon-silicon bonds are desdribed, e.g., in
British Pat. No. 1,090,589, may also be used as activators, e.g.,
2,2,4-trimethyl-1,2-silamorpholine or
1,3-diethylaminoethyl-tetramethyldisiloxane.
(d) Other examples of catalysts which may be used according to the
invention, and details of their action are described in
Kunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen,
Carl-Hanser-Verlag, Munich, 1966, on pages 96 and 102.
8. Water containing 1% to 10% by weight of bases which contain
nitrogen such as tetraalkyl ammonium hydroxides.
9. Water containing 1% to 10% by weight of alkali metal hydroxides
such as sodium hydroxide; alkali metal phenolates such as sodium
phenolate or alkali metal alcoholates such as sodium methylate.
10. Water containing sodium polysulfide in the amount of 1% to 10%
by weight.
11. Water containing 20% to 70% by weight of a water-binding agent,
being capable of absorbing water to form a solid or a gel, such as
hydraulic cement, synthetic anhydrite, gypsum or burnt lime.
12. Mixtures of the above-name curing agents.
Surface-active additives (emulsifiers and foam stabilizers) may
also be used according to the invention. Suitable emulsifiers are,
e.g., the sodium salts of ricinoleic sulphonates or of fatty acid,
or salts of fatty acids with amines, e.g., oleic acid diethylamine
or stearic acid diethanolamine. Other surface-active additives are
alkali metal or ammonium salts of sulphonic acids, e.g.,
dodecylbenzine sulphonic acid or dinaphthyl methane disulphonic
acid; or of fatty acids, e.g., ricinoleic acid, or of polymeric
fatty acids.
The foam stabilizers used are mainly water-soluble polyester
siloxanes. These compounds generally have a polydimethylsiloxane
group attached to a copolymer of ethylene oxide and propylene
oxide. Foam stabilizers of this kind have been described in U.S.
Pat. No. 3,629,308. These additives are, preferably, used in
quantities of up to 20%, based on the reaction mixture.
Negative catalyst, for example, substances which are acidic in
reaction, e.g., hydrochloric acid or organic acid halides, known
cell regulators, e.g., paraffins, fatty alcohols or dimethyl
polysiloxanes, pigments or dyes, know flame-retarding agents, e.g.,
tris-chloroethylphosphate or ammonium phosphate and polyphosphates,
stabilizers against aging and weathering, pasticizers, fungicidal
and bacteriocidal substances and fillers, e.g., barium sulphate,
kieselguhr, carbon black or whiting, may also be used according to
the invention.
Further examples of surface additives, foam stabilizers, cell
regulators, negative catalysts, stabilizers, flame-retarding
substances, plasticizers, dyes, fillers and fungicidal and
bacteriocidal substances and details about methods of using these
additives and their action may be found in Kunststoff-Handbuch,
Volume VI, published by Vieweg and Hochtlen, Carl-Hanser-Verlag,
Munich, 1966, on pages 103 to 113. The halogenated paraffins and
inorganic salts of phosphoric acid are the preferred fire-retarding
agents.
Aqueous solutions of silicates may be prepared in the form of 25%
to 70% silicates. Silica sols which may have an alkaline or acid pH
may also be used; they should have solid contents of 15% to 50%.
Silica sols are generally used in combination with aqueous silicate
solutions. The choice of concentration depends mainly on the
desired end product. Compact materials or materials with closed
cells are, preferably, produced with concentrated silicated
solutions which, if necessary, are adjusted to a lower viscosity by
addition of alkali metal hydroxide. Solutions with concentrations
of 40% to 70% by weight can be prepared in this way. On the other
hand, to produce open-celled light-weight foams, it is preferred to
use silicate solutions with concentrations of 20% to 45% by weight
in order to obtain low viscosities, sufficiently long reaction
times and low unit weights. Silicate solutions with concentrations
of 15% to 45% are also preferred when substantial quantities of
finely divided inorganic fillers are used.
Suitable flame-resistant compounds may be used in the products of
this invention such as those which contain halogen or phosphorus,
e.g., tributylphosphate; tris(2,3-dichloropropyl)-phosphate;
polyoxypropylenechloromethylphosphonate; cresylidiphenylphosphate;
tricresylphosphate; tris-(beta-chloroethyl)-phosphate;
tris-(2,3-dichloropropyl)-phosphate; triphenylphosphate; ammonium
phosphate; perchloroinated diphenyl phosphate; perchlorinated
terephenyl phosphate; hexabromocyclodecane; tribromophenol;
dibromopropyldiene; hexabromobenzene; octabromodiphenylether;
pentabromotoluol; polytribromostyrol; tris-(bromocresyl)-phosphate;
tetrabromobis-phenol A; tetrabromophthalic acid anhydride;
octabromodiphenyl phosphate; tri-(dibromopropyl)-phosphate; calcium
hydrogen phosphate; sodium or potassium dihydrogen phosphate;
disodium or dipotassium hydrogenphosphate; ammonium chloride,
phosphoric acid; polyvinylchloride tetomers chloroparaffins as well
as further phosphorus- and/or halogen-containing flame-resistant
compounds as they are described in Kunststoff-Handbuch, Volume VII,
Munich, 1966, pages 110 and 111, which are incorporated herein by
reference. The organic halogen-containing components are, however,
preferred in the polyurethane products.
The ratios of the essential reactants and optional reactants which
lead to the polyurethane resinous or foamed product of this
invention may vary, broadly speaking, with ranges as follows:
(a) 1 to 95 parts by weight of polyester resinous product,
preferably with free hydroxyl group and produced by the process of
this invention;
(b) 50 parts by weight of polyisocyanate, polyisocyanate or
isocyanate-terminated polyurethane prepolymer;
(c) up to 20% by weight of a foam stabilizer;
(d) up to 50% by weight of a chemically inert blowing agent,
boiling within the range of from -25.degree. C. to 80.degree.
C.;
(e) up to 10% by weight of an activator;
(f) up to 200 parts by weight of a water-binding agent;
(g) up to 95 parts by weight of a polyol.
Percentages are based on the weight of the reactants, polyester
resinous product, polyol and polyisocyanate.
In the cases where the viscosity of the polyisocyanate is too high,
it may be reduced by adding a low-viscosity isocyanate, or even by
adding inert solvents such as acetone, diethyl ether of diethylene
glycol, ethyl acetate and the like.
In cases where the curing agent contains an aqueous alkali
silicate, the isocyanate-terminated polyurethane prepolymer may be
sulphonated. It is usually sufficient to react the
isocyanate-terminated polyurethane prepolymer with concentrated
sulphuric acid or oleum of sulfur trioxide in order to produce a
sulphonated poly(urethane silicate) prepolymer containing the
sulphonic group in the amount of 3 to 100 milli-equivalents/100 g.
The reaction will take place by thoroughly mixing the sulphuric
acid or oleum or sulfur trioxide with the isocyanate-terminated
polyurethane prepolymer at ambient temperature and pressure. In
some cases where sulfur trioxide is used, an increased pressure is
advantageous. The polyisocyanate may be modified to contain ionic
groups before reacting with the polyester resinous products.
The sulphonated isocyanate-terminated polyurethane prepolymer can
be directly mixed with an aqueous silicate solution, in which case
the corresponding metal salt is formed in situ. The sulphonated
polyurethane prepolymer may be completely or partly neutralized at
the onset by the addition of amines metal alcoholates, metal
oxides, metal hydroxide or metal carbonates.
Water-binding components may be used in this invention, including
organic or inorganic water-binding substances which have, first,
the ability to chemically combine, preferably irreversibly, with
water and, second, the ability to reinforce the poly(urethane
silicate) plastics of the invention. The term "water-binding
component" is used herein to identify a material, preferably
granular or particulate, which is sufficiently anhydrous to be
capable of absorbing water to form a solid or gel such as mortar of
hydraulic cement.
A water-binding component such as hydraulic cement, synthetic
anhydrides, gypsum or burnt lime may be added to any of the
components to produce a tough, somewhat flexible solid or cellular
solid concrete. The water-binding component may be added in amounts
from 0 to 200% by weight, based on the weight of the reactants.
When a water-binding agent is added and when the curing agent is an
aqueous alkali metal silicate solution, a halogen- or
phosphorus-containing compound or mixture thereof may be added in
the amount of 1% to 30% by weight, based on the weight of the
reactants.
Suitable hydraulic cements are, in particular, Portland cement,
quick-setting cement, blast-furnace Portland cement, mild-burnt
cement, sulphate-resistant cement, brick cement, natural cement,
lime cement, gypsum cement, pozzolan cement and calcium sulphate
cement. In general, any mixture of fine ground lime, alumina and
silica that will set to a hard product by admixture of water, which
combines chemically with the other ingredients to form a hydrate,
may be used. There are many kinds of cement which can be used in
the production of the compositions of the invention and they are so
well known that a detailed description of cement will not be given
here; however, one can find such a detailed description in
Encyclopedia of Chemical Technology, Volume 4, Second Edition,
published by Kirk-Othmer, pages 684 to 710, of the type of cement
which may be used in the production of this invention and which are
incorporated herein by reference.
Blowing agents may be used to improve or increase the foaming to
produce cellular solid plastics such as acetone, ethyl acetate,
methanol, ethanol, halogenated alkanes, e.g., methylene chloride,
chloroform, ethylidene chloride, vinylidene chloride,
monofluorotrichloromethane, chlorodifluoromethane, butane, hexane
or diethyl ether. Compounds which decompose at temperatures above
room temperature with liberation of gases, e.g., nitrogen, such as
azo compounds, azoisobutyric acid nitrile, may also act as blowing
agents. Compressed air may act as a blowing agent. Other examples
of blowing agents and details of the use of blowing agents are
described in Kunststoff-Handbuch, Volume VII, published by Vieweg
and Hochtlen, Carl-Hanser-Verlag, Munich, 1966, e.g., on pages 108
and 109, 453 to 455 and 507 to 510.
The proportions of the components may be adjusted to a highly
cellular solid. When water is used, it reacts with the NCO group to
produce CO.sub.2 and pores are produced in the product by the
evolved CO.sub.2. In certain cases, the CO.sub.2 is rapidly evolved
and escapes before the product hardens, and a solid product can be
produced, nearly completely free of air cells. When a high silicate
content, from 80% to 99% by weight, is desirable, such as when the
final product is required to have mainly the properties of an
inorganic silicate plastic, in particular, high-temperature
resistance and complete flame resistance, an alkali metal silicate
may be added with copolymer or polyol or be reacted with the
polyisocyanate to produce a polyurethane prepolymer. In that case,
the function of the polyisocyanate is that of a non-volatile
hardener whose reaction product is a high-molecular-weight polymer
which reduces the brittleness of the product.
When an alkali catalyst or alkali metal silicate is used in the
invention, fine metal powders, e.g., powdered calcium, magnesium,
aluminum or zinc, may also act as the blowing agents by bringing
about the evolution of hydrogen. Compressed air may be mixed in the
components and may also be used to mix the components, then be used
as the blowing agent. These metal powders also have a hardening or
reinforcing effect.
The properties of the foams (cellular solid) obtained from any
given formulation, e.g., their density in the moist state, depends
to some extent on the details of the mixing process, e.g., the form
and speed of the stirrer and the form of the mixing chamber, and
also the selected temperature at which foaming is started. The
foams will usually expand 3 to 12 times their original volume.
The polyurethane plastics produced by the invention have many uses.
The reaction mixture, with or without a blowing agent, may be mixed
in a mixing apparatus; then the reaction mixture may be sprayed by
means of compressed air or by the airless spraying process onto
surfaces; subsequently, the mixture expands and hardens in the form
of a cellular solid which is useful for insulation, filling, and
moisture-proofing coating. The foaming material may also be forced,
poured or injection-molded into cold or heated molds, which may be
relief molds or solid or hollow molds, optionally by centrifugal
casting, and left to harden at room temperature or at temperatures
up to 200.degree. C., at ambient pressure or at elevated pressure.
In certain cases, it may be necessary to heat the mixing or
spraying apparatus to initiate foaming; then, once foaming has
started, the heat evolved by the reaction between components
continues the foaming until the reaction is complete. A temperature
between 40.degree. C. and 150.degree. C. may be required in order
to initiate foaming. The blowing agent may be added to the
polyisocyanate or polyester resinous product.
Reinforcing elements may quite easily be incorporated into the
reaction mixtures. The inorganic and/or organic reinforcing
elements may be, e.g., fibers, metal wires, foams, fabrics, fleeces
or skeletons. The reinforcing elements may be mixed with the
reaction mixtures, for example, by the fibrous web impregnation or
by processes in which the reaction mixtures and reinforcing fibers
are together applied to the mold, for example, by means of a spray
apparatus. The shaped products obtainable in this way may be used
as building elements, e.g., in the form of sandwich elements,
either as such or after they have been laminated with metal, glass
or plastics; if desired, these sandwich elements may be formed. The
products may be used as hollow bodies, e.g., as containers for
goods which may be required to be kept moist or cool, as filter
materials or exchanges, as catalyst carriers or carriers of other
active substances, as decorative elements, furniture components and
fillings or for cavities. They may be used in the field of model
building and mold building, and the production of molds for metal
casting may also be considered.
Instead of blowing agents, finely divided inorganic or organic
hollow particles, e.g., hollow expanded beads of glass, plastics
and straw, may be used for producing cellular solid products. These
products may be used as insulating materials, cavity fillings,
packaging materials, building materials which have good solvent
resistance and advantageous fire-resistant characteristics. They
may also be used as lightweight building bricks in the form of
sandwiches, e.g., with metal-covering layers for house building and
the construction of motor vehicles and aircraft.
Organic or inorganic particles which are capable of foaming up or
have already been foamed may be incorporated in the fluid foaming
reaction mixture, e.g., expanded clay, expanded glass, wood, cork,
popcorn, hollow plastic beads such as beads of vinyl chloride
polymers, polyethylene, styrene polymers, or foam particles of
these polymers or other polymers, e.g., polysulphone, polyepoxide,
polyurethane, poly(urethane silicate) copolymers,
urea-formaldehyde, phenol-formaldehyde or polyimide polymers, or,
alternatively, heaps of these particles may be permeated with
foaming reaction mixtures to produce insulation materials which
have good fire-resistant characteristics.
The cellular solid products of the invention, in the aqueous or dry
or impregnated state, may subsequently be lacquered metallized,
coated, laminated, galvanized, vapor-treated, bonded or blocked.
The cellular solid products may be sawed, drilled, planed,
polished, or other working processes may be used to produce shaped
products. The shaped products, with or without a filler, may be
further modified in their properties by subsequent heat treatment,
oxidation processes, hot pressing, sintering processes or surface
melting or other compacting processes.
The novel cellular solid products of the invention are also
suitable for use as constructional materials due to their toughness
and stiffness, yet they are still elastic. They are resistant to
tension and compression and have a high-dimensional stability to
heat and high flame resistance. They have excellent
sound-absorption capacity, heat-insulating capacity, fire
resistance, and heat resistance which makes them useful for
insulation. The cellular products of this invention may be foamed
on the building site and, in many cases, used in place of wood or
hard fiber boards. Any hollow forms may be used for foaming. The
brittle foams may be crushed and used as filler, as a soil
conditioner, as a substrate for the propagation of seedlings,
cuttings and plants or cut flowers.
The foamed or solid concrete produced by reaction of the organic
broken-down lignin cellulose polymer, polyol and polyisocyanate
with a water-binding component may be used as surface coatings
having wood adhesion and resistance-to-abrasion properties, as
mortars, and for making molded products, particularly in
construction engineering and civil engineering such as for building
walls, igloos, boats and for roadbuilding, etc. These products are
light-weight, thermal-insulating materials with excellent
mechanical properties and fire resistance. The amount of
water-binding component used varies greatly, depending on the type
of product desired, up to 200% by weight, based on weight of
reactants. In certain cases, it is desirable to add sand and gravel
in the amount of 1 to 6 parts by weight to each part by weight of
the hydraulic cement. The mixture may be poured in place, troweled
on or sprayed onto the desired surface to produce a solid or
cellular solid product.
Fillers in the form of powders, granules, wire, fibers,
dumb-bell-shaped particles, crystallites, spirals, rods, beads,
hollow beads, foam particles, non-woven webs, pieces of woven or
knitted fabrics, tapes and pieces of foil of solid inorganic or
organic substances, e.g., dolomite, chalk, alumina, asbestos, basic
silicic acids, sand, talc, iron oxides, aluminum oxide and
hydroxides, alkali metal silicates, zeolites, mixed silicates,
calcium silicate, calcium sulphates, aluminosilicates, cements,
basalt wool or powder, galss fibers, carbon fibers, graphite,
carbon black, Al-, Fe-, Cri- and Ag-powders, molybdenum sulphide,
steel wool, bronze or copper meshes, silicon powder, expanded clay
particles, hollow glass beads, glass powder, lava and pumice
particles, wood chips, woodmeal, cork, cotton, straw, popcorn, coke
or particles of filled or unfilled, foamed or unfoamed, stretched
or unstretched organic polymers, may be added to the mixture of the
Components (a), (b) and (c) in many applications. Among the
numerous organic polymers which may be used, e.g., as powders,
granules, foam particles, beads, hollow beads, foamable (but
not-yet-foamed) particles, fibers, tapes, woven fabrics, or
fleeces, the following may be mentioned as examples: Polystyrene,
polyethylene, polypropylene, polyacrylonitrile, polybutadiene,
polyisoprene, polytetrafluorethylene, aliphatic and aromatic
polyesters, melamine, urea, phenol resins, phenol silicate resins,
polyacetal resins, polyepoxides, polyhydantoins, polyureas,
polyethers, polyurethanes, polyimides, polyamides, polysulphones,
polycarbonates and copolymers thereof.
The composite materials, according to the invention, may be mixed
with considerable quantities of fillers without losing their
advantageous properties, and, in particular, composite materials
which consist predominantly of organic constituents which are
preferably filled with inorganic fillers; where silicate
constituents predominate, it is, preferably, filled with organic
fillers. Fillers which are particularly preferred are chalk, talc,
dolomite, gypsum, clay, anhydrite, glass, carbon and the
conventional plastics and rubber waste.
In the production of surface coatings, bonds, putties or
interlayers, particularly in the case of porous materials, it is
preferred to use polyisocyanates which have only a low isocyanate
content, e.g., less than 5%, or prepolymers which are free from
isocyanate groups. The mixtures obtained in this way have a long
pot life and may be applied in thin layers which gradually harden
in the course of time. The liberated CO.sub.2 acts as the curing
agent. In a two-stage or multistage hardening in which, for
example, an excess of water is used, there is a rapid evolution of
CO.sub.2 and the polyurethane silicon acid resinous product is
converted into a workable form which may be used as putties,
coating agents, grouting materials or mortar. This thermoplastic
form may also be injection-molded, extruded or worked up in a
kneader.
In many cases, the polyurethane resinous and foamed products
produced by the invention are soluble in organic solvents and may
be used as a tough coating agent for wood and metal. The mixtures
of the invention are also suitable for use as impregnating agents
for finishing fibers. The mixtures may also be extruded through
dies or slots and be converted into fibers and foils. These fibers
and foils may be used for producing synthetic incombustible paper
or fleeces.
When the polyester resinous product produced by the process of this
invention and polyisocyanate are combined with expanded clay and an
alkali metal silicate solution, a very good concrete is obtained
which can, for example, be used as panels in the construction
field. In this case, the foam material (expanded clay) plays the
part of the binding material.
The object of this invention is to provide a novel process for the
production of a polyester resinous product. Another object is to
produce a novel polyester resinous product. Another object is to
produce a novel polyester resinous product that will react with
polyisocyanates to produce useful polyurethane foams and solid
resinous products. Another object is to produce novel unsaturated
polyester resinous products.
DETAILED DESCRIPTION OF THE INVENTION
I have discovered that a polyester resinous product may be produced
by mixing 10 to 50 parts by weight of a broken-down alkali metal
lignin-cellulose polymer, 10 to 50 parts by weight of a substituted
organic hydroxy compound and a polycarboxylic acid and/or a
polycarboxylic acid anhydride, heating the mixture to just below
the boiling temperature of the reactants, then gradually increasing
the temperature up to 250.degree. C. while agitating for from 30
minutes to 4 hours.
The reaction of this invention may take place under any suitable
physical condition. While most of the reactions will take place at
ambient pressure, in certain cases, a pressure either lower than,
or above, ambient pressure may give the best result. It may be
preferable in certain cases to use temperature above the
substituted organic hydroxy compound's boiling temperature after a
partial reaction has taken place in order to speed up the chemical
reaction. The temperature usually ranges between 150.degree. C. and
250.degree. C., when the substituted organic compound is a gas,
elevated pressures are necessary.
The polyester resinous product may be modified by the addition of
the following components to the mixture of broken-down alkali metal
lignin-cellulose polymer, substituted organic hydroxy compound and
polycarboxylic acid and/or polycarboxylic acid anhydride:
(a) up to 25 parts by weight of an organic polyhydroxy compound
when 50 parts by weight of polycarboxylic acid or polycarboxylic
acid anhydride are utilized;
(b) up to 50% by weight of a vinyl monomer, percentage based on
polyester resinous product;
(c) up to 25 parts by weight of an aldehyde when 50 parts by weight
of broken-down alkali metal lignin-cellulose polymer are used.
(d) up to 25 parts by weight of a substituted organic compound when
50 parts by weight of broken-down alkali metal lignin-cellulose
polymer are used;
(e) up to 50% by weight of the polycarboxylic acid and/or
polycarboxylic acid anhydride may be replaced with a vegetable
oil;
(f) up to 25 parts by weight of water when 50 parts by weight of
the broken-down alkali metal lignin-cellulose are used.
The unsaturated polyester resinous product will react with vinyl
monomers in the presence of an initiator. The vinyl monomer may be
added in an amount up to 50% by weight, percentage based on the
polyester resinous product. Any suitable peroxide initiator may be
used, usually an amount of 0.2% to 0.5% by weight being a catalytic
amount, percentage based on weight of the polyester resinous
product. Any suitable activator may be used to activate the
peroxide initiator, in an amount of 30 to 100 ppm.
The polyester resinous products of this invention will react with
polyisocyanates and polyisothiocyanates to produce foamed and solid
polyurethane resinous products. The reaction will take place in any
suitable physical conditions. The reactions will usually take place
at ambient temperature or pressure, but in certain cases, an
elevated or lowered temperature or pressure is preferred.
DESCRIPTION OF PREFERRED EMBODIMENTS
My invention will be illustrated in greater detail by the specific
examples which follow, it being understood that these preferred
embodiments are illustrative of, but not limited to, procedures
which may be used in the production of polyester products. Parts
and percentages are by weight unless otherwise indicated.
EXAMPLE 1
About 2 parts by weight of fir sawdust and 1.5 parts by weight of
melted sodium hydroxide flakes (lye) are mixed, then heated to
between 150.degree. C. and 220.degree. C. while agitating at
ambient pressure for 5 to 60 minutes or until the mixture softens
and expands into a brown, thick liquid which solidifies on cooling,
thereby producing a broken-down sodium lignin-cellulose
polymer.
EXAMPLE 2
About 2 parts by weight of small plant particles listed below and 2
parts by weight of melted sodium hydroxide in the form of caustic
soda are mixed, then heated to between 150.degree. C. and
220.degree. C. while agitating at ambient pressure, with care being
taken to avoid burning the mixture, for 5 to 60 minutes; the
mixture begins to expand and a brown, thick, liquid, broken-down
sodium lignin-cellulose polymer is produced. The liquid solidifies
on cooling and is ground into a powder. The powder is soluble in
water, alcohols, polyhydric organic compounds and other
solvents.
______________________________________ (a) Oak sawdust; (g) Cotton
stalks; (b) Fir sawdust; (h) Bagasse; (c) Ash sawdust; (i) Equal
parts paper and (d) Seaweed; fir sawdust; (e) Equal parts cotton
(j) Oat straw; and fir sawdust; (k) Grass clippings. (f) Corn cobs;
______________________________________
EXAMPLE 3
About 1 part by weight of melted lye flakes (NaOH) and 2 parts by
weight of fir sawdust are mixed, then heated to between 150.degree.
C. and 220.degree. C. while agitating at ambient pressure, with
care being taken that the mixture does not burn, for 5 to 60
minutes or unitl the mixture softens and expands into a dark-brown,
thick liquid when hot. It cools to a solid, thereby producing a
broken-down alkali metal plant polymer which is water-soluble and
has lost a CO.sub.2 radical per molecule.
Other plant particles may be used in place of fir sawdust, such
as:
______________________________________ (a) Oak sawdust; (h) Paper;
(b) Ash sawdust; (i) Oat straw; (c) Seaweed; (j) Grass clippings;
(d) Cotton; (k) Pine sawdust; (e) Corn cobs; (l) Equal parts of
paper (f) Cotton stalks; and fir sawdust. (g) Bagasse;
______________________________________
4 parts by weight of the broken-down alkali metal plant polymer are
mixed with 4 parts by weight of an aqueous solution containing 37%
formaldehyde, then heated to between 70.degree. C. and 100.degree.
C. while agitating for 30 to 120 minutes, thereby producing alkali
metal formaldehyde lignin-cellulose polymer.
EXAMPLE 4
About equal parts by weight of melted sodium hydroxide in the form
of caustic soda and a plant particle listed below are mixed, then
heated to between 150.degree. C. and 220.degree. C. while agitating
at ambient pressure for 5 to 60 minutes or until the mixture
softens and expands into a thick, brown liquid which solidifies on
cooling, thereby producing a broken-down alkali metal plant
polymer. The polymer is ground into small particles.
______________________________________ (a) Fir sawdust; (j) Equal
mixture of (b) Oak sawdust; (a) and cotton; (c) Beech sawdust; (k)
Pine sawdust; (d) Redwood sawdust; (l) Maple sawdust; (e) Gum
sawdust; (m) Elm sawdust; (f) Sigmore sawdust; (n) Corn cob
particles; (g) Cotton stalk particles; (o) Seaweed particles; (h)
Mixture of weed (p) Cornstalk particles; particles; (q) Bugasse
particles; (i) Equal mixture of (a) (r) Mixtures thereof. and
newspapers; ______________________________________
About 2 parts by weight of the broken-down alkali metal plant
polymer and 1 part by weight of acetaldehyde are mixed, then heated
to between 70.degree. C. and 100.degree. C. while agitating for 30
to 120 minutes, thereby producing alkali metal acetaldehyde
lignin-cellulose polymer.
EXAMPLE 5
About equal parts by weight of melted potassium hydroxide and a
plant particle selected from the list below are mixed, then heated
to between 150.degree. C. and 220.degree. C. while agitating at
ambient pressure for 5 to 60 minutes or until the mixture softens
and expands, thereby producing alkali metal lignin-cellulose
polymer.
EXAMPLE 6
About 10 parts by weight of broken-down alkali metal
lignin-cellulose as produced in Example 2b are dissolved in
ethanol, then butane-1-hydrogen sulfate is slowly added, in an
amount wherein the hydrogen sulfate radicals are about equal to the
sodium radicals, while agitating for about 30 minutes. The reaction
is complete in 30 minutes to 8 hours, thereby producing a brown
organic lignin-cellulose polymer.
Other substituted organic compounds may be used in place of
butane-1-hydrogen sulfate such as para chlorobenzene;
2-nitrotoluene; 1-chloro-2-propanol; methyl sulfate;
1,1-bromopropane; ethyl sulfate; 1-bromo-2-butene; ethylene
chlorohydrin; ethyl hydrogen sulfate; dichloroacetic acid;
p-chlorobenzyl and mixtures thereof.
EXAMPLE 7
About 10 parts by weight of the broken-down sodium lignin-cellulose
polymer as produced in 2b and 10 parts by weight of polyethylene
glycol (mol. wt. 380 to 420) are mixed and heated until the polymer
goes into solution; then ethyl chloride is slowly added in an
autoclave at 1000 to 1500 psi in an amount wherein the chlorine
atoms about equal the sodium atoms while agitating at a temperature
between 150.degree. C. and 200.degree. C. for about 30 minutes,
thereby producing an ethyl lignin-cellulose polymer.
EXAMPLE 8
The broken-down alkali lignin-cellulose polymer produced in Example
2f is mixed with ethyl acetate in about equal amounts while
agitating for about 30 minutes, thereby producing a broken-down
organic lignin-cellulose polymer. The polymer is recovered by
filtration.
EXAMPLE 9
Propane -1-dihydrogen phosphate is slowly added to a broken-down
alkali metal cellulose polymer as produced in Example 2h in an
amount wherein the phosphate radicals are about equivalent to the
sodium radicals while agitating at a temperature just below the
boiling temperature of the reactants for 30 minutes. The reaction
is complete in 30 minutes to 8 hours, thereby producing a propyl
lignin-cellulose polymer.
EXAMPLE 10
About 3 parts by weight of a broken-down alkali metal
lignin-cellulose, as produced in Example 2f are ground into a fine
powder, then bis-monochloroacetic acid, in the amount wherein the
chlorine atoms are about equal to the sodium atoms in the mixture,
is slowly added while agitating at a temperature just below the
boiling temperature of monochloroacetic acid for about 30 minutes.
The reaction is complete in 30 minutes to 8 hours, thereby
producing a carboxymethyl lignin-cellulose polymer.
EXAMPLE 11
About 10 parts by weight of the broken-down sodium lignin-cellulose
polymer as produced in Example 1, 10 parts by weight of ethylene
chlorohydrin and 15 parts by weight of phthalic anhydride are
mixed, then heated to just below the boiling temperature of
ethylene chlorohydrin while agitating and the temperature is slowly
increased to about 200.degree. C. while continuing to agitate for
from 30 minutes to 4 hours, thereby producing a brown, solid,
polyester resinous product and salt.
EXAMPLE 12
About 10 parts by weight of the broken-down sodium lignin-cellulose
polymer as produced in Example 2a, 10 parts by weight of ethylene
chlorohydrin, 5 parts by weight of phthalic anhydride, 5 parts by
weight of adipic acid and 5 parts by weight of maleic acid are
mixed, then slowly heated to just below the boiling point of the
reactants; then, as the boiling point is elevated, the mixture is
heated at about 220.degree. C. while agitating for from 30 minutes
to 4 hours, thereby producing an unsaturated polyester resinous
product and salt.
EXAMPLE 13
About 10 parts by weight of broken-down sodium lignin-cellulose
polymer as produced in Example 2i, 5 parts by weight of ethylene
chlorohydrin, 5 parts by weight of glycerine, .alpha., .gamma.
dichlorohydrin, by parts by weight of phthalic anhydride and 10
parts by weight of linseed oil are mixed, then heated to just below
the boiling temperature of the reactants while agitating and
gradually increasing the temperature up to 220.degree. C.,
continuing to agitate for 30 minutes to 4 hours, thereby producing
a brown, solid polyester resinous product and salt.
EXAMPLE 14
About 10 parts by weight of the broken-down sodium lignin-cellulose
polymer as produced in Example 2e, 10 parts by weight of ethylene
chlorohydrin, 5 parts by weight of propylene glycol, 10 parts by
weight of maleic anhydride, 5 parts by weight of phthalic anhydride
and 10 parts by weight of adipic acid are mixed, then heated to a
temperature just below the boiling temperature of propylene glycol,
with a slow increase in the temperature up to 220.degree. C. while
agitating for from 30 minutes to 4 hours; thereby producing a
brown, solid polyester resinous product.
EXAMPLE 15
About 20 parts by weight of the polyester resinous product as
produced in Example 14, while at about 90.degree. C., are mixed
with 10 parts by weight of styrene, thereby producing a liquid
unsaturated polyester resinous product.
About 25 to 100 ppm of cobalt, in the form of cobalt naphthanate,
are mixed with 20 parts by weight of the liquid unsaturated
polyester resinous product, then 0.2% to 0.5% by weight of methyl
ethyl ketone peroxide, percentage based on polyester resinous
product, is added to the mixture, agitating well. The mixture is
then applied to multiple layers of fiberglas and cures in from 30
minutes to 2 hours, thereby producing a polyester panel which may
be used in construction, boats, aircraft, etc.
EXAMPLE 16
About 10 parts by weight of the sodium formaldehyde
lignin-cellulose polymer as produced in Example 3, 5 parts by
weight of chloroacetic acid, 10 parts by weight of broken-down
lignin-cellulose as produced in Example 2b, 10 parts by weight of
ethylene chlorohydrin, 5 parts by weight of glycerol, 10 parts by
weight of phthalic anhydride and 10 parts by weight of adipic acid
are mixed, then heated to just below the boiling temperature of the
reactants while agitating, then gradually increasing the
temperature to 220.degree. C. for from 30 minutes to 4 hours,
thereby producing a brown, solid polyester resinous product.
The polyester resinous product may be molded by heat and pressure
to produce useful objects such as knobs, panels, art objects,
etc.
EXAMPLE 17
About 20 parts by weight of the broken-down sodium lignin-cellulose
polymer as produced in Example 2b, 20 parts by weight of ethylene
chlorohydrin, 5 parts by weight of trimethylol ethane and 5 parts
by weight of allyl chloride are mixed, then 10 parts by weight of
phthalic anhydride, 5 parts by weight of adipic acid and 10 parts
by weight of xylene are added. The mixture is placed in a reactor
with a reflux condenser, then heated to about 150.degree. C. while
agitating. As the reaction proceeds, the temperature is gradually
increased up to 250.degree. C. and the mixture is agitated for from
30 minutes to 4 hours, thereby producing a brown, semi-solid
polyester resinous product.
EXAMPLE 18
About 100 parts by weight of the polyester resinous product as
produced in Example 17 are mixed with 100 parts by weight of a
polyisocyanate listed below. The mixture slowly hardens to form a
brown, solid polyurethane product.
______________________________________ Example Polyisocyanate
______________________________________ a Tolylene diisocyanate; b
Methylene bis-phenyl diisocyanate; c 4,4-diphenylmethylene
diisocyanate; d Polyphenyl polymethylene-isocyanate (crude MDI)
with an NCO content by weight of 31; e Equal parts by weight of
tolylene diisocyanate and polyphenyl polymethylene-isocyanates with
an NCO content by weight of about 31.
______________________________________
EXAMPLE 19
Example 18 is modified wherein 5 parts by weight of ethylene
chloride, 5 parts by weight of trichlorotrifluoroethane, 0.5 part
by weight of triethanolamine, 0.5 part by weight of triethylamine,
0.1 part by weight of tin octoate and 0.5 part by weight of a
silicone surfactant (L-5420 produced by Union Carbide) are mixed
with the polyester resinous product, then reacted with the selected
polyisocyanate, thereby producing a rigid polyurethane foam
product.
EXAMPLE 20
Example 18 is modified wherein 10 parts by weight of aqueous sodium
silicate (SiO.sub.2 :NaO ratio of 2:1 and containing 40% solids)
are mixed with the polyester resinous product, then reacted with
the polyisocyanate, thereby producing a polyurethane silicate
product.
EXAMPLE 21
Example 19 is modified wherein 25 parts by weight of a
60%-by-weight aqueous sodium silicate solution, with an SiO.sub.2
:NaO ratio of 1.6:1, are added with the components of Example 19,
then mixed with the selected polyisocyanate, thereby producing a
rigid polyurethane silicate foam product.
EXAMPLE 22
About 100 parts by weight of the polyester resinous product as
produced in Example 14 and 100 parts by weight of an
isocyanate-terminated polyurethane prepolymer listed below are
mixed and slowly reacted to produce a solid polyurethane
product.
______________________________________ Ex- am- ple
Isocyanate-terminated polyurethane prepolymer
______________________________________ a
Polyphenyl-polymethylene-isocyanates with an NCO content of about
31 reacted with 5% acetic acid; b
Polyphenyl-polymethylene-isocyanates with an NCO content of about
31 reacted with 1% propylene glycol; c
Polyphenyl-polymethylene-isocyanates with an NCO content of about
31 reacted with 2% polypropylene glycol (mol. wt. 380); d Toluene
diisocyanate with polypropylene glycol (mol. wt. 500) in an NCO/OH
ratio of 25:1; e Diisocyanato-diphenylmethane with a
tetra-functional polypropylene glycol (mol. wt. 500) to produce a
prepolymer having about 22% NCO groups; f Toluene diisocyanate with
castor oil to produce a prepolymer with an NCO content of about
15%; g Toluene diisocyanate with a hydroxyl-group-contain- ing
polysulfide polymer to produce a prepolymer with an NCO content of
about 12%; h Methylene bis-phenol diisocyanate with a liquid
polyepichlorohydrin to produce a prepolymer of about 16%, and 25%
by weight of a resin extender, polyalphamethyl-styrene, are added,
percentage based on weight of prepolymer; i Tolylene diisocyanate
with a polyester (4 mols of glycerol, 2.5 mols of adipic acid and
0.5 mol of phthalic anhydride) to produce a prepolymer with an NCO
content of about 23%; j Tolylene diisocyanate with polyethylene
glycol (mol. wt. 2000) to produce a prepolymer with an NCO content
of about 28%. ______________________________________
EXAMPLE 23
Example 22 is modified wherein 10 parts by weight of
trichlorofluoromethane, 0.5 part by weight of triethylenediamine,
0.05 part by weight of tin octoate, 1 part by weight of sodium
doctyl sulfosuccinate and 0.5 part by weight of a silicone
surfactant (L-5420 produced by Union Carbide) are mixed with the
polyester resinous product of Example 22, then mixed and reacted at
ambient temperature and pressure, thereby producing a polyurethane
foam.
EXAMPLE 24
Claim 18 is modified wherein 50 parts by weight of a surcose amine
polyol (mol. wt. about 2000) and 50 parts by weight of Portland
cement are added with the polyester resinous product, then 100
parts by weight of Portland cement are mixed with the
polyisocyanate listed. The components are mixed, thereby producing
a polyurethane product.
EXAMPLE 25
About 25 parts by weight of the polyester resinous product as
produced in Example 11, 50 parts by weight of amine sucrose polyol
(mol. wt. 2000), 25 parts by weight of an aqueous sodium silicate
solution containing 60% solids (SiO.sub.2 :NaO ratio of 1.6:1), 1
part by weight of a silicone surfactant (L-5420 produced by Union
Carbide) and 0.2 part by weight of tin diacetate are thoroughly
mixed, then 100 parts by weight of Portland cement are admixed with
the mixture, then 100 parts by weight of a phosgenation product of
aniline-formaldehyde condensation, with an NCO content of about
31%, are added and thoroughly mixed. The mixture expands to produce
a rigid, foamed polyurethane concrete.
Other water-binding agents may be used in place of Portland cement,
such as other hydraulic cements, burnt lime, gypsum and synthetic
anhydrites.
EXAMPLE 26
Example 13 is modified wherein 3 parts by weight of water are added
to the broken-down sodium lignin-cellulose.
EXAMPLE 27
About 100 parts by weight of the unsaturated polyester resinous
product in styrene as produced in Example 15, 0.1 part by weight of
cobalt naphthanate, 0.2 part by weight of benzoyl peroxide, 0.2
part by weight of methyl ethyl ketone, 10 parts by weight of
trichlorotrifluoroethane, 0.5 part by weight of a silicone
surfactant (L-5420 produced by Union Carbide) and 1 part by weight
of triethylenediamine are mixed, then the mixture is mixed with 100
parts by weight of 4,4-diphenylmethane diisocyanate. The mixture
begins to expand in from 30 to 120 seconds, thereby producing a
rigid polyurethane foam.
EXAMPLE 28
About 25 parts by weight of the broken-down sodium lignin-cellulose
polymer as produced in Example 21, 10 parts by weight of aqueous
solution containing 37% formaldehyde by weight, 5 parts by weight
of ethyl hydrogen sulfate, and 10 parts by weight of ethylene
chlorohydrin are mixed and reacted at ambient temperature and
pressure for about 30 minutes, then 30 parts by weight of phthalic
anhydride are added and the mixture is heated to about 150.degree.
C. while agitating; then the temperature is gradually increased to
about 220.degree. C. The reaction is complete in from 30 minutes to
4 hours, thereby producing polyester resinous product.
Other substituted compounds may be used in place of ethyl hydrogen
sulfate such as ethyl sulfate, ethylene chloride, vinylidene
chloride, methyl methacrylate, vinyl acetate, acetic anhydride,
sodium chloroacetate, chloroform, methylene chloride,
1-nitropropane, dichloroacetic acid, methyl allyl chloride, allyl
chloride, methyl acetate, trichloromesitylene, trichlorobutylene
oxide, epichlorohydrin, methyl octalate and mixtures thereof.
Although specific materials and conditions were set forth in the
above Examples, these were merely illustrative of preferred
embodiments of my invention. Various other compositions, such as
the typical materials listed above, may be used where suitable. The
reactive mixtures and products of my invention may have other
agents added thereto in order to enhance or otherwise modify the
reaction and products. Other modifications of my invention will
occur to those skilled in the art upon reading my disclosure. These
are intended to be included within the scope of my invention, as
defined in the appended Claims.
* * * * *